ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES

Abstract

Provided are organometallic compounds comprising two or more carbene atoms coordinated to Pt(II) or Pd(II), wherein the compound may comprise at least one deuterium atom. Also provided are formulations comprising these organometallic compounds. Further provided are organic light emitting devices (OLEDs) and related consumer products that utilize these organometallic compounds.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 63/483,761, filed on Feb. 8, 2023, the entire contents of which are incorporated herein by reference.

FIELD

The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.

SUMMARY

In one aspect, a compound comprising two or more carbene atoms coordinated to Pt(II) or Pd(II); and wherein the compound comprises at least one deuterium atom.

In another aspect, the present disclosure provides a monometallic compound comprising a tetradentate ligand L_A, wherein: L_A is coordinated to a metal M selected from the group consisting of Pt, Pd, Cu, Ag, and Au; L_A comprises a first moiety and a second moiety; the first moiety and the second moiety are both heterocyclic carbene ligands, which coordinate to M through metal-carbene bonds; wherein at least the first moiety comprises Formula I as defined herein.

In yet another aspect, the present disclosure provides a compound comprising a first ligand L_A′ of Formula II as defined herein.

In yet another aspect, the present disclosure provides a formulation of the compound as described herein.

In yet another aspect, the present disclosure provides an OLED having an organic layer comprising the compound as described herein.

In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising the compound as described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

DETAILED DESCRIPTION

A. Terminology

Unless otherwise specified, the below terms used herein are defined as follows:

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

Layers, materials, regions, and devices may be described herein in reference to the color of light they emit. In general, as used herein, an emissive region that is described as producing a specific color of light may include one or more emissive layers disposed over each other in a stack.

As used herein, a “NIR”, “red”, “green”, “blue”, “yellow” layer, material, region, or device refers to a layer, a material, a region, or a device that emits light in the wavelength range of about 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, 540-600 nm, respectively, or a layer, a material, a region, or a device that has a highest peak in its emission spectrum in the respective wavelength region. In some arrangements, separate regions, layers, materials, or devices may provide separate “deep blue” and “light blue” emissions. As used herein, the “deep blue” emission component refers to an emission having a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of the “light blue” emission component. Typically, a “light blue” emission component has a peak emission wavelength in the range of about 465-500 nm, and a “deep blue” emission component has a peak emission wavelength in the range of about 400-470 nm, though these ranges may vary for some configurations.

In some arrangements, a color altering layer that converts, modifies, or shifts the color of the light emitted by another layer to an emission having a different wavelength is provided. Such a color altering layer can be formulated to shift wavelength of the light emitted by the other layer by a defined amount, as measured by the difference in the wavelength of the emitted light and the wavelength of the resulting light. In general, there are two classes of color altering layers: color filters that modify a spectrum by removing light of unwanted wavelengths, and color changing layers that convert photons of higher energy to lower energy. For example, a “red” color filter can be present in order to filter an input light to remove light having a wavelength outside the range of about 580-700 nm. A component “of a color” refers to a component that, when activated or used, produces or otherwise emits light having a particular color as previously described. For example, a “first emissive region of a first color” and a “second emissive region of a second color different than the first color” describes two emissive regions that, when activated within a device, emit two different colors as previously described.

As used herein, emissive materials, layers, and regions may be distinguished from one another and from other structures based upon light initially generated by the material, layer or region, as opposed to light eventually emitted by the same or a different structure. The initial light generation typically is the result of an energy level change resulting in emission of a photon. For example, an organic emissive material may initially generate blue light, which may be converted by a color filter, quantum dot or other structure to red or green light, such that a complete emissive stack or sub-pixel emits the red or green light. In this case the initial emissive material, region, or layer may be referred to as a “blue” component, even though the sub-pixel is a “red” or “green” component.

In some cases, it may be preferable to describe the color of a component such as an emissive region, sub-pixel, color altering layer, or the like, in terms of 1931 CIE coordinates. For example, a yellow emissive material may have multiple peak emission wavelengths, one in or near an edge of the “green” region, and one within or near an edge of the “red” region as previously described. Accordingly, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. The shape in 1931 CIE color space is constructed by following the locus between two color points and any additional interior points. For example, interior shape parameters for red, green, blue, and yellow may be defined as shown below:

Color          CIE Shape Parameters
Central Red    Locus: [0.6270, 0.3725]; [0.7347, 0.2653];
               Interior: [0.5086, 0.2657]
Central Green  Locus: [0.0326, 0.3530]; [0.3731, 0.6245];
               Interior: [0.2268, 0.3321
Central Blue   Locus: [0.1746, 0.0052]; [0.0326, 0.3530];
               Interior: [0.2268, 0.3321]
Central Yellow Locus: [0.3731, 0.6245]; [0.6270, 0.3725];
               Interior: [0.3700, 0.4087]; [0.2886, 0.4572]

The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.

The term “acyl” refers to a substituted carbonyl group (—C(O)—R_s).

The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R_s or —C(O)—O—R_s) group.

The term “ether” refers to an —OR_s group.

The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SR_s group.

The term “selenyl” refers to a —SeR_s group.

The term “sulfinyl” refers to a —S(O)—R_s group.

The term “sulfonyl” refers to a —SO₂—R_s group.

The term “phosphino” refers to a group containing at least one phosphorus atom bonded to the relevant structure. Common examples of phosphino groups include, but are not limited to, groups such as a —P(R_s)₂ group or a —PO(R_s)₂ group, wherein each R_s can be same or different.

The term “silyl” refers to a group containing at least one silicon atom bonded to the relevant structure. Common examples of silyl groups include, but are not limited to, groups such as a —Si(R_s)₃ group, wherein each R_s can be same or different.

The term “germyl” refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germyl groups include, but are not limited to, groups such as a —Ge(R_s)₃ group, wherein each R_s can be same or different.

The term “boryl” refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boryl groups include, but are not limited to, groups such as a —B(R_s)₂ group or its Lewis adduct —B(R_s)₃ group, wherein R_s can be same or different.

In each of the above, R_s can be hydrogen or a substituent selected from the group consisting of the general substituents as defined in this application. Preferred R_s is selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. More preferably R_s is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.

The term “alkyl” refers to and includes both straight and branched chain alkyl groups having an alkyl carbon atom bonded to the relevant structure. Preferred alkyl groups are those containing from one to fifteen carbon atoms, preferably one to nine carbon atoms, and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group can be further substituted.

The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl groups having a ring alkyl carbon atom bonded to the relevant structure. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group can be further substituted.

The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl group, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, Ge and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group can be further substituted.

The term “alkenyl” refers to and includes both straight and branched chain alkene groups. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain with one carbon atom from the carbon-carbon double bond that is bonded to the relevant structure. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl group having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, Ge, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group can be further substituted.

The term “alkynyl” refers to and includes both straight and branched chain alkyne groups. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain with one carbon atom from the carbon-carbon triple bond that is bonded to the relevant structure. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group can be further substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an aryl-substituted alkyl group having an alkyl carbon atom bonded to the relevant structure. Additionally, the aralkyl group can be further substituted.

The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably, O, S, N, or B. Hetero-aromatic cyclic groups may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 10 ring atoms, preferably those containing 3 to 7 ring atoms, which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group can be further substituted or fused.

The term “aryl” refers to and includes both single-ring and polycyclic aromatic hydrocarbyl groups. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”). Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons, twelve carbons, fourteen carbons, or eighteen carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, and naphthalene. Additionally, the aryl group can be further substituted or fused, such as, without limitation, fluorene.

The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, Se, N, P, B, Si, Ge, and Se. In many instances, O, S, N, or B are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more aromatic rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborine, borazine, 51²,91²-diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ²-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 51²,91²-diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ²-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene. Additionally, the heteroaryl group can be further substituted or fused.

Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 51²,91²-diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ²-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, and the respective aza-analogs of each thereof are of particular interest.

In many instances, the General Substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In some instances, the Preferred General Substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

In some instances, the More Preferred General Substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, aryl, heteroaryl, nitrile, sulfanyl, and combinations thereof.

In some instances, the Even More Preferred General Substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.

In yet other instances, the Most Preferred General Substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R¹ represents mono-substitution, then one R¹ must be other than H (i.e., a substitution). Similarly, when R¹ represents di-substitution, then two of R¹ must be other than H. Similarly, when R¹ represents zero or no substitution, R¹, for example, can be a hydrogen for all available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.

As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.

The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.

As used herein, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. includes undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also include undeuterated, partially deuterated, and fully deuterated versions thereof. Unless otherwise specified, atoms in chemical structures without valences fully filled by H or D should be considered to include undeuterated, partially deuterated, and fully deuterated versions thereof. For example, the chemical structure of

implies to include C₆H₆, C₆D₆, C₆H₃D₃, and any other partially deuterated variants thereof. Some common basic partially or fully deuterated group include, without limitation, CD₃, CD₂C(CH₃)₃, C(CD₃)₃, and C₆D₅.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.

In some instances, a pair of substituents in the molecule can be optionally joined or fused into a ring. The preferred ring is a five to nine-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. In yet other instances, a pair of adjacent substituents can be optionally joined or fused into a ring. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2,2′ positions in a biphenyl, or 1,8 position in a naphthalene.

B. The Compounds of the Present Disclosure

In one aspect, the present disclosure provides a compound comprising two or more carbene atoms coordinated to Pt(II) or Pd(II); and wherein the compound comprises at least one deuterium atom.

In some embodiments, the compound is not:

In some embodiments, the two or more carbene atoms are coordinated to Pt(II).

In some embodiments, the two or more carbene atoms are coordinated to Pd(II).

In some embodiments, the two carbene atoms are comprised by a tridentate ligand.

In some embodiments, the two carbene atoms are comprised by a tetradentate ligand.

In some embodiments, the two carbene atoms are comprised by an N-heterocyclic carbene ligand.

In some embodiments, the two carbene atoms are trans.

In some embodiments, the two carbene atoms are cis.

In some embodiments, the compound comprises four metal-carbon bonds.

In some embodiments, the compound comprises at least one metal-oxygen bond.

In some embodiments, the compound comprises two metal-oxygen bonds.

In some embodiments, the compound comprises at least one deuterated alkyl group or deuterated phenyl group.

In some embodiments, the compound comprises at least one fully deuterated alkyl group or fully deuterated phenyl group.

In some embodiments, the compound comprises at least one fully deuterated methyl group.

In some embodiments, the compound comprises at least one fully deuterated phenyl group.

In some embodiments, the compound has a C₂-axis of rotation.

In some embodiments, the compound has mirror symmetry.

In some embodiments, the compound also comprises an electron-withdrawing group. In some embodiments, the electron-withdrawing group has a Hammett constant larger than 0. In some embodiments, the electron-withdrawing group has a Hammett constant equal or larger than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.

In some embodiments, the compound comprises an electron-withdrawn group selected from the group consisting of the structures of the following EWG1 LIST: F, CF₃, CN, COCH₃, CHO, COCF₃, COOMe, COOCF₃, NO₂, SF₃, SiF₃, PF₄, SF₅, OCF₃, SCF₃, SeCF₃, SOCF₃, SeOCF₃, SO₂F, SO₂CF₃, SeO₂CF₃, OSeO₂CF₃, OCN, SCN, SeCN, NC, ⁺N(R^k2)₃, (R^k2)₂CCN, (R^k2)₂CCF₃, CNC(CF₃)₂, BR^k3R^k2, substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridoxine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

• • wherein each R^k1 represents mono to the maximum allowable substitution, or no substitutions;
  • wherein Y^G is selected from the group consisting of BR_e, NR_e, PR_e, O, S, Se, C═O, S═O, SO₂, CR_eR_f, SiR_eR_f, and GeR_eR_f; and
  • wherein each of R^k1, R^k2, R^k3, R_e, and R_f is independently a hydrogen or a substituent selected from the group consisting of the General Substituents defined herein.

In some embodiments, the compound comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG2 List:

In some embodiments, the compound comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG3 LIST:

In some embodiments, the compound comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG4 LIST:

In some embodiments, the compound comprises an electron-withdrawing group that is a π-electron deficient electron-withdrawing group. In some embodiments, the π-electron deficient electron-withdrawing group is selected from the group consisting of the structures of the following Pi-EWG LIST: CN, COCH₃, CHO, COCF₃, COOMe, COOCF₃, NO₂, SF₃, SiF₃, PF₄, SFs, OCF₃, SCF₃, SeCF₃, SOCF₃, SeOCF₃, SO₂F, SO₂CF₃, SeO₂CF₃, OSeO₂CF₃, OCN, SCN, SeCN, NC, ⁺N(R^k2)₃, BR^k2R^k3, substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,

wherein the variables are the same as previously defined.

In some embodiments, the compound is selected from the group consisting of:

wherein R^A, R^B, R^C, R^D, and R^E each independently represent mono to the maximum allowable substitution, or no substitution;
wherein each of R, R′, R^A, R^B, R^C, R^D, and R^E is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;
wherein X¹—X⁵ are each independently C or N;
L is selected from the group consisting of a direct bond, BR, BRR′, NR, PR, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO₂, CR, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; each of L¹ and L² is independently absent or selected from the group consisting of BR, BRR′, NR, PR, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO₂, CR, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;
any two substituents can be joined or fused to form a ring; and
at least one of R, R′, R^A, R^B, R^C, R^D, and R^E is or comprises a deuterium atom.

In some embodiments, each R, R′, R^A, R^B, R^C, R^D, and R^E is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

In some embodiments where the compound has R, at least one R is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments where the compound has R, at least one R is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments where the compound has R, at least one R is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein.

In some embodiments where the compound has R, at least one R is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments where the compound has R, at least one R is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments where the compound has R′, at least one R′ is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments where the compound has R′, at least one R′ is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments where the compound has R′, at least one R′ is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments where the compound has R′, at least one R′ is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments where the compound has R′, at least one R′ is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments where the compound has R^A, at least one R^A is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments where the compound has R^A, at least one R^A is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments where the compound has R^A, at least one R^A is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments where the compound has R^A, at least one R^A is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments where the compound has R^A, at least one R^A is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments where the compound has R^B, at least one R^B is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments where the compound has R^B, at least one R^B is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments where the compound has R^B, at least one R^B is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments where the compound has R^B, at least one R^B is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments where the compound has R^B, at least one R^B is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments where the compound has R^C, at least one R^C is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments where the compound has R^C, at least one R^C is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments where the compound has R^C, at least one R^C is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments where the compound has R^C, at least one R^C is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments where the compound has R^C, at least one R^C is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments where the compound has R^D, at least one R^D is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments where the compound has R^D, at least one R^D is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments where the compound has R^D, at least one R^D is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments where the compound has R^D, at least one R^D is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments where the compound has R^D, at least one R^D is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments where the compound has R^E, at least one R^E is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments where the compound has R^E, at least one R^E is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments where the compound has R^E, at least one R^E is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments where the compound has R^E, at least one R^E is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments where the compound has R^E, at least one R^E is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments, L¹ is absent.

In some embodiments, L² is absent.

In some embodiments, one of L¹ and L² is absent.

In some embodiments, both L¹ and L² are absent.

In some embodiments, L¹ is CRR′ or SiRR′.

In some embodiments, L² is CRR′ or SiRR′.

In some embodiments, L¹ and L² are each CRR′ or each SiRR′.

In some embodiments, L is a direct bond.

In some embodiments, L is O.

In some embodiments, the compound comprises a deuterated methyl group or a deuterated phenyl group.

In some embodiments, the compound comprises a fully deuterated methyl group or a fully deuterated phenyl group.

In some embodiments, the ligand L_A is selected from the group consisting of L_Aw (Ri)(Lm)(Ln)(Lo), wherein w is an integer from 1 to 8, Ri is R1 from R445 as defined in LIST 5, Lm, Ln, Lo, Lp are each independently from L1 to L29 as defined LIST 6, and each L_Aw (Ri)(Lm)(Ln)(Lo) is defined below:

TABLE A
LA Structure of LA
LA1-(Ri)(Lm)(Ln), wherein LA1-(R1)(L1)(L1) to LA1-(R445)(L29)(L29), having the structure
LA2-(Ri)(Lm)(Ln), wherein LA2-(R1)(L1)(L1) to LA2-(R445)(L29)(L29), having the structure
LA3-(Ri)(Lm)(Ln), wherein LA3-(R1)(L1)(L1) to LA3-(R445)(L29)(L29), having the structure
LA4-(Ri)(Lm)(Ln), wherein LA4-(R1)(L1)(L1) to LA4-(R445)(L29)(L29), having the structure
LA5-(Ri)(Lm)(Ln)(Lo), wherein LA5- (R1)(L1)(L1)(L1) to LA5- (R445)(L29)(L29)(L29), having the structure
LA6-(Ri)(Lm)(Ln)(Lo), wherein LA6- (R1)(L1)(L1)(L1) to LA6- (R445)(L29)(L29)(L29), having the structure
LA7-(Ri)(Lm)(Ln)(Lo), wherein LA7- (R1)(L1)(L1)(L1) to LA7- (R445)(L29)(L29)(L29), having the structure
LA8-(Ri)(Lm)(Ln)(Lo), wherein LA8- (R1)(L1)(L1)(L1) to LA8- (R445)(L29)(L29)(L29), having the structure

In some of the above embodiments, the metal is Pt.

In some embodiments, the compound is selected from the group consisting of:

In another aspect, the present disclosure provides a monometallic compound comprising a tetradentate ligand L_A, wherein:

L_A is coordinated to a metal M, which is selected from the group consisting of Pt, Pd, Cu, Ag, and Au;
L_A comprises a first moiety and a second moiety;
the first moiety and the second moiety are both heterocyclic carbene ligands, which coordinate to M through metal-carbene bonds;
wherein at least the first moiety comprises Formula I:

wherein the dashed line indicates a carbene bond to M;
wherein the wavy line indicates the remaining part of the tetradentate ligand L_A;
wherein R^A and R^B each independently represent mono to the maximum allowable substitution, or no substitution;
wherein each R^A and R^B is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;
wherein X¹—X⁵ are each independently C or N;
wherein X¹—X⁵ is C if attached to an R^A substituent and
wherein any two substituents may be joined or fused to form a ring.

In some embodiments, at least one R^A is selected from the group consisting of deuterium, deuterated alkyl, aryl, heteroaryl, cycloalkyl, and cycloheteroalkyl, and combinations thereof, and is attached to X¹ or X⁵.

In some embodiments, at least one R^A comprises deuterium, silicon, boron, or selenium.

In some embodiments, the compound does not comprise the structure:

wherein R is a methyl or a phenyl group.

In some embodiments, at least one R^B comprises at least one deuterium atom. In some embodiments, the compound comprises at least one deuterium atom.

In some embodiments, the ring formed by the any two substituents which may be joined or fused to from a ring, is a 5-membered or 6-membered aryl or heteroaryl. In some embodiments, the formed ring can be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, fluorene, or aza-fluorene. In some embodiments, the aza variant includes one N on a benzo ring.

It should be understood that the 5-membered or the 6-membered aryl or heteroaryl as described above are applicable to any two substituents that are joined or fused throughout this disclosure, and the individual rings described above are also applicable to the formed ring between any two substituents throughout this disclosure.

In some embodiments, each R^A and R^B is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

In some embodiments, at least three of X¹—X⁵ are C.

In some embodiments, all of X¹—X⁵ are C.

In some embodiments, at least one of X¹—X⁵ is N.

In some embodiments, wherein at least one R^A is different from hydrogen.

In some embodiments, all R^A are hydrogen or deuterium.

In some embodiments, all R^A are hydrogen.

In some embodiments, at least one R^A is silyl.

In some embodiments, at least one R^B is different from hydrogen.

In some embodiments, all R^B are hydrogen.

In some embodiments, two R^B are joined to form a ring.

In some embodiments, two R^B are joined to form a 6-membered aromatic ring.

In some embodiments, the ligand L_A is selected from the group consisting of:

wherein each L is independently selected from LIST 1 consisting of:

wherein each L¹ and L² is independently selected from LIST 2 consisting of:
absent,

wherein R^A, R^B, R^C, R^D, and R^E each independently represent mono to the maximum allowable substitution, or no substitution;
wherein each R, R′, R^A, R^B, R^C, R^D, and R^E is independently selected from LIST 3 consisting of:

In some embodiments, at least one of R, R′, R^A, R^B, R^C, R^D, and R^E is independently selected from LIST 4 consisting of:

wherein each of Q^A, Q^B, Q^C, Q^D and Q^E independently represents mono to the maximum allowable substitution, or no substitution;
wherein each Q^A, Q^B, Q^C, Q^D, Q^E, Q^A1, Q^B1, Q^C1, Q^D1 and Q^E1 is independently a hydrogen or a substituent selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof; each Y^aa and Y^bb is independently selected from the group consisting of a direct bond, BR, BRR′, NR, PR, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO₂, CR, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and any two substituents can be joined or fused to form a ring.

In some embodiments, the ligand L_A is selected from the group consisting of the following structures:

TABLE B
LA Structure of LA
LA9-(Ri)(Rj)(Lm)(Ln), wherein LA9- (R29)(R1)(L1)(L1) to LA9- (R445)(R445)(L29)(L29), having the structure
LA10- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA10- (R29)(R1)(R1)(L1)(L1) to LA10- (R445)(R445)(R445)(L29) (L29), having the structure
LA11- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA11- (R29)(R1)(R1)(L1)(L1) to LA11- (R445)(R445)(R445)(L29) (L29), having the structure
LA12-(Ri)(Rj)(Lm)(Ln), wherein LA12- (R29)(R1)(L1)(L1) to LA12- (R445)(R445)(L29)(L29), having the structure
LA13- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA13- (R29)(R1)(R1)(L1)(L1) to LA13- (R445)(R445)(R445)(L29) (L29), having the structure
LA14- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA14- (R29)(R1)(R1)(L1)(L1) to LA14- (R445)(R445)(R445)(L29) (L29), having the structure
LA15-(Ri)(Rj)(Lm)(Ln), wherein LA15- (R29)(R1)(L1)(L1) to LA15- (R445)(R445)(L29)(L29), having the structure
LA16- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA16- (R29)(R1)(R1)(L1)(L1) to LA16- (R445)(R445)(R445)(L29) (L29), having the structure
LA17- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA17- (R29)(R1)(R1)(L1)(L1) to LA17- (R445)(R445)(R445)(L29) (L29), having the structure
LA18-(Ri)(Rj)(Lm)(Ln), wherein LA18- (R29)(R1)(L1)(L1) to LA18- (R445)(R445)(L29)(L29), having the structure
LA19- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA19- (R29)(R1)(R1)(L1)(L1) to LA19- (R445)(R445)(R445)(L29) (L29), having the structure
LA20- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA20- (R29)(R1)(R1)(L1)(L1) to LA20- (R445)(R445)(R445)(L29) (L29), having the structure
LA21- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA21- (R1)(R1)(R1)(L1)(L1) to LA21- (R445)(R445)(R445)(L29) (L29), having the structure
LA22- (Ri)(Rj)(Rk)(RI)(Lm)(Ln), wherein LA22- (R1)(R1)(R1)(R1)(L1)(L1) to LA22- (R445)(R445)(R445)(R445) (L29)(L29), having the structure
LA23- (Ri)(Rj)(Rk)(RI)(Lm)(Ln), wherein LA23- (R29)(R1)(R1)(R1)(L1)(L1) to LA23- (R445)(R445)(R445)(R445) (L29)(L29), having the structure
LA24- (Ri)(Rj)(Rk)(R/)(Lm)(Ln), wherein LA24- (R29)(R1)(R1)(R1)(L1)(L1) to LA24- (R445)(R445)(R445)(R445) (L29)(L29), having the structure

TABLE C
LA Structure of LA
LA25-(Rp)(Rj)(Lm)(Ln), wherein LA25- (R203)(R1)(L1)(L1) to LA25- (R445)(R445)(L29)(L29), having the structure
LA26-(Rp)(Rj)(Lm)(Ln), wherein LA26- (R203)(R1)(L1)(L1) to LA26- (R445)(R445)(L29)(L29), having the structure
LA27-(Rp)(Rj)(Lm)(Ln), wherein LA27- (R203)(R1)(L1)(L1) to LA27- (R445)(R445)(L29)(L29), having the structure
LA28-(Rp)(Rj)(Lm)(Ln), wherein LA28- (R203)(R1)(L1)(L1) to LA28- (R445)(R445)(L29)(L29), having the structure
LA29-(Rp)(Rj)(Lm)(Ln), wherein LA29- (R203)(R1)(L1)(L1) to LA29- (R445)(R445)(L29)(L29), having the structure
LA30-(Rp)(Rj)(Lm)(Ln), wherein LA30- (R203)(R1)(L1)(L1) to LA30- (R445)(R445)(L29)(L29), having the structure
LA31-(Rp)(Rj)(Lm)(Ln), wherein LA31- (R203)(R1)(L1)(L1) to LA31- (R445)(R445)(L29)(L29), having the structure
LA32-(Rp)(Rj)(Lm)(Ln), wherein LA32- (R203)(R1)(L1)(L1) to LA32- (R445)(R445)(L29)(L29), having the structure
LA33-(Rp)(Rj)(Lm)(Ln), wherein LA33- (R203)(R1)(L1)(L1) to LA33- (R445)(R445)(L29)(L29), having the structure
LA34-(Rp)(Rj)(Lm)(Ln), wherein LA34- (R203)(R1)(L1)(L1) to LA34- (R445)(R445)(L29)(L29), having the structure
LA35-(Rp)(Rj)(Lm)(Ln), wherein LA35- (R203)(R1)(L1)(L1) to LA35- (R445)(R445)(L29)(L29), having the structure
LA36-(Rp)(Rj)(Lm)(Ln), wherein LA36- (R203)(R1)(L1)(L1) to LA36- (R445)(R445)(L29)(L29), having the structure

wherein i, j, k, and l, are each independently an integer from 1 to 445, and p is an integer from 203 to 445, wherein R1 to R445 have the following structures (LIST 5):

Structure
R1
R2
R3
R4
R5
R6
R7
R8
R9
R10
R11
R12
R13
R14
R15
R16
R17
R18
R19
R20
R21
R22
R23
R24
R25
R26
R27
R28
R29
R30
R31
R32
R33
R34
R35
R36
R37
R38
R39
R40
R41
R42
R43
R44
R45
R46
R47
R48
R49
R50
R51
R52
R53
R54
R55
R56
R57
R58
R59
R60
R61
R62
R63
R64
R65
R66
R67
R68
R69
R70
R71
R72
R73
R74
R75
R76
R77
R78
R79
R80
R81
R82
R83
R84
R85
R86
R87
R88
R89
R90
R91
R92
R93
R94
R95
R96
R97
R98
R99
R100
R101
R102
R103
R104
R105
R106
R107
R108
R109
R110
R111
R112
R113
R114
R115
R116
R117
R118
R119
R120
R121
R122
R123
R124
R125
R126
R127
R128
R129
R130
R131
R132
R133
R134
R135
R136
R137
R138
R139
R140
R141
R142
R143
R144
R145
R146
R147
R148
R149
R150
R151
R152
R153
R154
R155
R156
R157
R158
R159
R160
R161
R162
R163
R164
R165
R166
R167
R168
R169
R170
R171
R172
R173
R174
R175
R176
R177
R178
R179
R180
R181
R182
R183
R184
R185
R186
R187
R188
R189
R190
R191
R192
R193
R194
R195
R196
R197
R198
R199
R200
R201
R202
R203
R204
R205
R206
R207
R208
R209
R210
R211
R212
R213
R214
R215
R216
R217
R218
R219
R220
R221
R222
R223
R224
R225
R226
R227
R228
R229
R230
R231
R232
R233
R234
R235
R236
R237
R238
R239
R240
R241
R242
R243
R244
R245
R246
R247
R248
R249
R250
R251
R252
R253
R254
R255
R256
R257
R258
R259
R260
R261
R262
R263
R264
R265
R266
R267
R268
R269
R270
R271
R272
R273
R274
R275
R276
R277
R278
R279
R280
R281
R282
R283
R284
R285
R286
R287
R288
R289
R290
R291
R292
R293
R294
R295
R296
R297
R298
R299
R300
R301
R302
R303
R304
R305
R306
R307
R308
R309
R310
R311
R312
R313
R314
R315
R316
R317
R318
R319
R320
R321
R322
R323
R324
R325
R326
R327
R328
R329
R330
R331
R332
R333
R334
R335
R336
R337
R338
R339
R340
R341
R342
R343
R344
R345
R346
R347
R348
R349
R350
R351
R352
R353
R354
R355
R356
R357
R358
R359
R360
R361
R362
R363
R364
R365
R366
R367
R368
R369
R370
R371
R372
R373
R374
R375
R376
R377
R378
R379
R380
R381
R382
R383
R384
R385
R386
R387
R388
R389
R390
R391
R392
R393
R394
R395
R396
R397
R398
R399
R400
R401
R402
R403
R404
R405
R406
R407
R408
R409
R410
R411
R412
R413
R414
R415
R416
R417
R418
R419
R420
R421
R422
R423
R424
R425
R426
R427
R428
R429
R430
R431
R432
R433
R434
R435
R436
R437
R438
R439
R440
R441
R442
R443
R444
R445

wherein m and n are each independently an integer from 1 to 29, wherein L1 to L29 have the following structures (LIST 6):

    Structure
L1
L2
L3
L4
L5
L6
L7
L8
L9
L10
L11
L12
L13
L14
L15
L16
L17
L18
L19
L20
L21
L22
L23
L24
L25
L26
L27
L28
L29 absence

In some of the embodiments of Table A and Table B, the metal is Pt.

In some embodiments, the compound is selected from the group consisting of:

In yet another aspect, the present disclosure provides a compound comprising a first ligand L_A′ of Formula II:

wherein R^F, R^G, and R^H each independently represent mono to the maximum allowable substitution, or no substitution;
wherein each R¹, R², R^F, R^G, and R^H is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;
wherein X⁶—X⁸ are each independently C or N;
L_A′ is coordinated to a metal M via the dashed lines, which is selected from the group consisting of Pt, Pd, Cu, Ag, and Au;
wherein at one of R¹ and R² is coordinated to M such that L_A′ is a tetradentate ligand; and
wherein any two substituents may be joined or fused to form a ring.

In some embodiments, at least one R¹, R², R^F, R^G, and R^H comprises at least one deuterium atom. In some embodiments, the compound comprises at least one deuterium atom.

In some embodiments of Formula II, R¹ is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, R¹ is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, R¹ is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, R¹ is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. I In some embodiments, R¹ is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments of Formula II, R² is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, R² is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, R² is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, R² is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. I In some embodiments, R² is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments of Formula II, at least one R^F is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R^F is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R^F is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R^F is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R^F is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments of Formula II, at least one R^G is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R^G is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R^G is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R^G is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R^G is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments of Formula II, at least one R^H is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R^H is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R^H is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R^H is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R^H is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.

In some embodiments, each R¹, R², R^F, R^G, and R^H is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

In some embodiments, at least one of X⁶—X⁸ is N.

In some embodiments, all of X⁶—X⁸ are C.

In some embodiments, all R^F or all R^G are hydrogen.

In some embodiments, all R^F and all R^G are hydrogen.

In some embodiments, two R^F or two R^G are joined to form a ring.

In some embodiments, two R^F or two R^G are joined to form a 5-membered or 6-membered aromatic ring.

In some embodiments, two R^F are joined to form a ring and two R^G are joined to form a 5-membered or 6-membered aromatic ring.

In some embodiments, two R^F are joined to form a 5-membered or 6-membered aromatic ring and two R^D are joined to form a 5-membered or 6-membered aromatic ring.

In some embodiments, the 5-membered or 6-membered aromatic ring can be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole. In some embodiments, the 6-membered can be benzene.

In some embodiments, all R^H are hydrogen.

In some embodiments, at least one R^H is different from hydrogen.

In some embodiments, one of R¹ and R² is alkyl.

In some embodiments, one of R¹ and R² is methyl.

In some embodiments, the first ligand L_A′ contains at least one 7, 8, 9, or 10-membered ring.

In some embodiments, the first ligand L_A′ contains at least one 7, 8, 9, or 10-membered aryl or heteroaryl ring.

In some embodiments, the at least one 7, 8, 9, or 10-membered aryl or heteroaryl ring can be further substituted.

In some embodiments, one or more pairs of the substituents can be joined to form a ring fused to the at least one 7, 8, 9, or 10-membered aryl or heteroaryl ring.

In some embodiments, the ligand L_A is selected from the group consisting of:

wherein K is selected from the group consisting of single bond, O, S, N(Rα), P(Rα), B(Rα), C(Rα)(Rβ), and Si(Rα)(Rβ);
wherein R^I represents mono to the maximum allowable substitution, or no substitution;
wherein each R^I is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;
wherein each L³, L⁴, and L⁵ is independently selected from LIST 2; wherein each R^F, R^G, R^H, R^I, and R′ is independently selected from LIST 3 and LIST 4;
the remaining variables are the same as previously defined, and
any two substituents can be joined or fused to form a ring.

In some embodiments, at least one of L⁴-L⁶ is not absent.

In some embodiments, at least two of L⁴-L⁶ are not absent.

In some embodiments, all of L⁴-L⁶ are absent.

In some embodiments, K is O.

In some embodiments, K is S.

In some embodiments, K is a single bond.

In some embodiments, all of R^F are hydrogen.

In some embodiments, all of R^G are hydrogen.

In some embodiments, all of R^H are hydrogen.

In some embodiments, all of R^I are hydrogen.

In some embodiments, all of R^F, R^G, R^H, and R^I are hydrogen.

In some embodiments, the ligand L_A′ is selected from the group consisting of:

LA′ Structure of LA′
LA′1-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′1- (R1)(R1)(L1)(L1)(L1) to LA′1- (R445)(R445)(L29)(L29)(L29), having the structure
LA′2-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′2- (R1)(R1)(L1)(L1)(L1) to LA′2- (R445)(R445)(L29)(L29)(L29), having the structure
LA′3-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′3- (R1)(R1)(L1)(L1)(L1) to LA′3- (R445)(R445)(L29)(L29)(L29), having the structure
LA′4-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′4- (R1)(R1)(R1)(L1)(L1)(L1) to LA′4- (R445)(R445)(R445)(L29)(L29)(L29), having the structure

wherein u and v are each independently an integer from 1 to 445, wherein R1 to R445 have the structures in LIST 5;
and wherein q, r, and s are each independently an integer from 1 to 29, wherein L1 to L29 have the structures in LIST 6.

In some embodiments, the compound is selected from the group consisting of:

In some embodiments, the compound described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen, deuterium, or halogen) that are replaced by deuterium atoms.

C. The OLEDs and the Devices of the Present Disclosure

In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer comprises a compound comprising two or more carbene atoms and at least one deuterium atom; or a compound comprising a tetradentate ligand L_A, wherein L_A comprises a first moiety and a second moiety; the first moiety and the second moiety are both heterocyclic carbene ligands, and wherein at least the first moiety comprises Formula I as defined herein; or a compound comprising a first ligand L_A′ of Formula II as defined herein.

In some embodiments, the organic layer is selected from the group consisting of HIL, HTL, EBL, EML, HBL, ETL, and EIL. In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.

In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ²-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, azaborinine, oxaborinine, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiine, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ²-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

In some embodiments, the host can be selected from the group consisting of the structures of the following HOST Group 1:

wherein:

• • each of J₁ to J₆ is independently C or N;
  • L′ is a direct bond or an organic linker;
  • each Y^AA, Y^BB, Y^CC, and Y^DD is independently selected from the group consisting of absent a bond, direct bond, O, S, Se, CRR′, SiRR′, GeRR′, NR, BR, BRR′;
  • each of R^A′, R^B′, R^C′, R^D′, R^E′, R^F′, and R^G′ independently represents mono, up to the maximum substitutions, or no substitutions;
  • each R, R′, R^A′, R^B′, R^C′, R^D′, R^E′, R^F′, and R^G′ is independently a hydrogen or a substituent selected from the group consisting of the General Substituents as defined herein; any two substituents can be joined or fused to form a ring;
  • and where possible, each unsubstituted aromatic carbon atom is optionally replaced with N to form an aza-substituted ring.

In some embodiments at least one of J₁ to J₃ is N. In some embodiments at least two of J₁ to J₃ are N. In some embodiments, all three of J₁ to J₃ are N. In some embodiments, each Y^CC and Y^DD is independently O, S, or SiRR′, or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced with N to form an aza-ring.

In some embodiments, the host is selected from the group consisting of EG1-MG1-EG1 to EG53-MG27-EG53 with a formula of EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 with a formula of EGa-EGc when MGb is absent, wherein a is an integer from 1 to 53, b is an integer from 1 to 27, c is an integer from 1 to 53. The structure of EG1 to EG53 is shown below:

The structure of MG1 to MG27 is shown below:

In some embodiments, the host can be any of the aza-substituted variants thereof, fully or partially deuterated variants thereof, and combinations thereof. In some embodiments, the host has formula selected from the HOST Group 2 consisting of h1 to h112.

	h	MGb	EGa	EGc
	h1	MG1	EG3	EG36
	h2	MG1	EG8	EG12
	h3	MG1	EG13	EG14
	h4	MG1	EG13	EG18
	h5	MG1	EG13	EG25
	h6	MG1	EG13	EG36
	h7	MG1	EG22	EG36
	h8	MG1	EG25	EG46
	h9	MG1	EG27	EG46
	h10	MG1	EG27	EG48
	h11	MG1	EG32	EG50
	h12	MG1	EG35	EG46
	h13	MG1	EG36	EG45
	h14	MG1	EG36	EG49
	h15	MG1	EG40	EG45
	h16	MG2	EG3	EG36
	h17	MG2	EG25	EG31
	h18	MG2	EG31	EG33
	h19	MG2	EG36	EG45
	h20	MG2	EG36	EG46
	h21	MG3	EG4	EG36
	h22	MG3	EG34	EG45
	h23	MG4	EG13	EG17
	h24	MG5	EG13	EG45
	h25	MG5	EG17	EG36
	h26	MG5	EG18	EG36
	h27	MG6	EG17	EG17
	h28	MG7	EG43	EG45
	h29	MG8	EG1	EG28
	h30	MG8	EG6	EG7
	h31	MG8	EG7	EG7
	h32	MG8	EG7	EG11
	h33	MG9	EG1	EG43
	h34	MG10	4-EG1	2-EG37
	h35	MG10	4-EG1	2-EG38
	h36	MG10	EG1	EG42
	h37	MG11	4-EG1	2-EG39
	h38	MG12	1-EG17	9-EG31
	h39	MG13	3-EG17	9-EG4
	h40	MG13	3-EG17	9-EG13
	h41	MG13	3-EG17	9-EG31
	h42	MG13	3-EG17	9-EG45
	h43	MG13	3-EG17	9-EG46
	h44	MG13	3-EG17	9-EG48
	h45	MG13	3-EG17	9-EG49
	h46	MG13	3-EG32	9-EG31
	h47	MG13	3-EG44	9-EG3
	h48	MG14	3-EG13	5-EG45
	h49	MG14	3-EG23	5-EG45
	h50	MG15	EG3	EG48
	h51	MG15	EG17	EG31
	h52	MG15	EG31	EG36
	h53	MG16	EG17	EG17
	h54	MG17	EG17	EG17
	h55	MG18	EG16	EG24
	h56	MG18	EG16	EG30
	h57	MG18	EG20	EG41
	h58	MG19	EG16	EG29
	h59	MG20	EG1	EG31
	h60	MG20	EG17	EG18
	h61	MG21	EG23	EG23
	h62	MG22	EG1	EG45
	h63	MG22	EG1	EG46
	h64	MG22	EG3	EG46
	h65	MG22	EG4	EG46
	h66	MG22	EG4	EG47
	h67	MG22	EG9	EG45
	h68	MG23	EG1	EG3
	h69	MG23	EG1	EG6
	h70	MG23	EG1	EG14
	h71	MG23	EG1	EG18
	h72	MG23	EG1	EG19
	h73	MG23	EG1	EG23
	h74	MG23	EG1	EG51
	h75	MG23	EG2	EG18
	h76	MG23	EG3	EG3
	h77	MG23	EG3	EG4
	h78	MG23	EG3	EG5
	h79	MG23	EG4	EG4
	h80	MG23	EG4	EG5
	h81	MG24	2-EG1	10-EG33
	h82	MG24	2-EG4	10-EG36
	h83	MG24	2-EG21	10-EG36
	h84	MG24	2-EG23	10-EG36
	h85	MG25	2-EG1	9-EG33
	h86	MG25	2-EG3	9-EG36
	h87	MG25	2-EG4	9-EG36
	h88	MG25	2-EG17	9-EG27
	h89	MG25	2-EG17	9-EG36
	h90	MG25	2-EG21	9-EG36
	h91	MG25	2-EG23	9-EG27
	h92	MG25	2-EG23	9-EG36
	h93	MG26	EG1	EG9
	h94	MG26	EG1	EG10
	h95	MG26	EG1	EG21
	h96	MG26	EG1	EG23
	h97	MG26	EG1	EG26
	h98	MG26	EG3	EG3
	h99	MG26	EG3	EG9
	h100	MG26	EG3	EG23
	h101	MG26	EG3	EG26
	h102	MG26	EG4	EG10
	h103	MG26	EG5	EG10
	h104	MG26	EG6	EG10
	h105	MG26	EG10	EG10
	h106	MG26	EG10	EG14
	h107	MG26	EG10	EG15
	h108	MG27	EG52	EG53
	h109	—	EG13	EG18
	h110	—	EG17	EG31
	h111	—	EG17	EG50
	h112	—	EG40	EG45

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

In some embodiments, the emissive layer can comprise two hosts, a first host and a second host. In some embodiments, the first host is a hole transporting host, and the second host is an electron transporting host. In some embodiments, the first host is a hole transporting host, and the second host is a bipolar host. In some embodiments, the first host is an electron transporting host, and the second host is a bipolar host. In some embodiments, the first host and the second host can form an exciplex. In some embodiments, the emissive layer can comprise a third host. In some embodiments, the third host is selected from the group consisting of an insulating host (wide band gap host), a hole transporting host, and an electron transporting host. In some embodiments, the third host forms an exciplex with one of the first host and the second host, or with both the first host and the second host. In some embodiments, the emissive layer can comprise a fourth host. In some embodiments, the fourth host is selected from the group consisting of an insulating host (wide band gap host), a hole transporting host, and an electron transporting host. In some embodiments, the fourth host forms an exciplex with one of the first host, the second host, and the third host, with two of the first host, the second host, and the third host, or with each of the first host, the second host, and the third host. In some embodiments, the electron transporting host has a LUMO less than −2.4 eV, less than −2.5 eV, less than −2.6 eV, or less than −2.7 eV. In some embodiments, the hole transporting host has a HOMO higher than −5.6 eV, higher than −5.5 eV, higher than −5.4 eV, or higher than −5.35 eV. The HOMO and LUMO values can be determined using solution electrochemistry. Solution cyclic voltammetry and differential pulsed voltammetry can be performed using a CH Instruments model 6201B potentiostat using anhydrous dimethylformamide (DMF) solvent and tetrabutylammonium hexafluorophosphate as the supporting electrolyte. Glassy carbon, platinum wire, and silver wire were used as the working, counter and reference electrodes, respectively. Electrochemical potentials can be referenced to an internal ferrocene-ferrocenium redox couple (Fc/Fc+) by measuring the peak potential differences from differential pulsed voltammetry. The corresponding highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies can be determined by referencing the cationic and anionic redox potentials to ferrocene (4.8 eV vs. vacuum) according to literature ((a) Fink, R.; Heischkel, Y.; Thelakkat, M.; Schmidt, H.-W. Chem. Mater. 1998, 10, 3620-3625. (b) Pommerehne, J.; Vestweber, H.; Guss, W.; Mahrt, R. F.; Bassler, H.; Porsch, M.; Daub, J. Adv. Mater. 1995, 7, 551).

In some embodiments, the compound as described herein may be a sensitizer or a component of a sensitizer; wherein the device may further comprise an acceptor that receives the energy from the sensitizer. In some embodiments, the acceptor is an emitter in the device. In some embodiments, the acceptor may be a fluorescent material. In some embodiments, the compound described herein can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contain an acceptor in the form of one or more non-delayed fluorescent and/or delayed fluorescence material. In some embodiments, the compound described herein can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 99.9%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a thermally activated delayed fluorescence (TADF) material. In some embodiments, the acceptor is a non-delayed fluorescent material. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter. In some embodiments, the acceptor has an emission at room temperature with a full width at half maximum (FWHM) of equal to or less than 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5 nm. Narrower FWHM means better color purity for the OLED display application.

As used herein, phosphorescence generally refers to emission of a photon with a change in electron spin quantum number, i.e., the initial and final states of the emission have different electron spin quantum numbers, such as from T1 to S0 state. Most of the Ir and Pt complexes currently used in OLED are phosphorescent emitters. In some embodiments, if an exciplex formation involves a triplet emitter, such exciplex can also emit phosphorescent light. On the other hand, fluorescent emitters generally refer to emission of a photon without a change in electron spin quantum number, such as from S1 to S0 state, or from D1 to D0 state. Fluorescent emitters can be delayed fluorescent or non-delayed fluorescent emitters. Depending on the spin state, fluorescent emitter can be a singlet emitter or a doublet emitter, or other multiplet emitter. It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. There are two types of delayed fluorescence, i.e. P-type and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA). On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the thermal population between the triplet states and the singlet excited states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as TADF. E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that TADF emissions require a compound or an exciplex having a small singlet-triplet energy gap (ΔE_S-T) less than or equal to 400, 350, 300, 250, 200, 150, 100, or 50 meV. There are two major types of TADF emitters, one is called donor-acceptor type TADF, the other one is called multiple resonance (MR) TADF. Often, single compound donor-acceptor TADF compounds are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings or cyano-substituted aromatic rings. Donor-acceptor exciplexes can be formed between a hole transporting compound and an electron transporting compound. Examples of MR-TADF materials include highly conjugated fused ring systems. In some embodiments, MR-TADF materials comprises boron, carbon, and nitrogen atoms. Such materials may comprise other atoms, such as oxygen, as well. In some embodiments, the reverse intersystem crossing time from T1 to Si of the delayed fluorescent emission at 293K is less than or equal to 10 microseconds. In some embodiments, such time can be greater than 10 microseconds and less than 100 microseconds.

In some embodiments, the OLED may comprise an additional compound selected from the group consisting of a non-delayed fluorescence material, a delayed fluorescence material, a phosphorescent material, and combination thereof.

In some embodiments, the inventive compound described herein is a phosphorescent material.

In some embodiments, the phosphorescent material is an emitter which emits light within the OLED. In some embodiments, the phosphorescent material does not emit light within the OLED. In some embodiments, the phosphorescent material energy transfers its excited state to another material within the OLED. In some embodiments, the phosphorescent material participates in charge transport within the OLED. In some embodiments, the phosphorescent material is a sensitizer or a component of a sensitizer, and the OLED further comprises an acceptor. In some embodiments, the phosphorescent material forms an exciplex with another material within the OLED, for example a host material, an emitter material.

In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material is an emitter which emits light within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material does not emit light within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material energy transfers its excited state to another material within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material participates in charge transport within the OLED. In some embodiments, the non-delayed fluorescence material or the delayed fluorescence material is an acceptor, and the OLED further comprises a sensitizer.

In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metal complex. In some embodiments, the delayed fluorescence material is a Pt, Pd, Zn, Cu, Ag, or Au complex (some of them are also called metal-assisted (MA) TADF). In some embodiments, the metal-assisted delayed fluorescence material comprises a metal-carbene bond. In some embodiments, the non-delayed fluorescence material or delayed fluorescence material comprises at least one chemical group selected from the group consisting of aryl-amine, aryloxy, arylthio, triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ²-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, 5□2,9□2-diaza-13b-boranaphtho[2,3,4-de]anthracene, 5-oxa-9□²-aza-13b-boranaphtho[3,2,1-de]anthracene, azaborinine, oxaborinine, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiine, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, amino, silyl, aza-variants thereof, and combinations thereof. In some embodiments, non-delayed the fluorescence material or delayed fluorescence material comprises a tri(aryl/heteroaryl)borane with one or more pairs of the substituents from the aryl/heteroaryl being joined to form a ring. In some embodiments, the fluorescence material comprises at least one chemical group selected from the group consisting of naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene.

In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound or a formulation of the compound as disclosed in the above compounds section of the present disclosure. In some embodiments, the emissive region can comprise a compound or a formulation of the compound comprising two or more carbene atoms and at least one deuterium atom; or the compound comprising a tetradentate ligand L_A, wherein L_A comprises a first moiety and a second moiety; the first moiety and the second moiety are both heterocyclic carbene ligands, and wherein at least the first moiety comprises Formula I as defined herein; or the compound comprising a first ligand L_A′ of Formula II as defined herein.

In some embodiments, the emissive region consists of one or more organic layers, wherein at least one of the one or more organic layers has a minimum thickness selected from the group consisting of 350, 400, 450, 500, 550, 600, 650 and 700 Å. In some embodiments, the at least one of the one or more organic layers are formed from an Emissive System that has a figure of merit (FOM) value equal to or larger than the number selected from the group consisting of 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 5.00, 10.0, 15.0, and 20.0. The definition of FOM is available in U.S. patent Application Publication No. 2023/0292605, and its entire contents are incorporated herein by reference. In some embodiments, the at least one of the one or more organic layers comprises a compound or a formulation of the compound as disclosed in Sections A and D of the present disclosure.

In some embodiments, the OLED or the emissive region comprising the inventive compound disclosed herein can be incorporated into a full-color pixel arrangement of a device. The full-color pixel arrangement of such device comprises at least one pixel, wherein the at least one pixel comprises a first subpixel and a second subpixel. The first subpixel includes a first OLED comprising a first emissive region. The second subpixel includes a second OLED comprising a second emissive region. In some embodiments, the first and/or second OLED, the first and/or second emissive region can be the same or different and each can independently have the various device characteristics and the various embodiments of the inventive compounds included therein, and various combinations and subcombinations of the various device characteristics and the various embodiments of the inventive compounds included therein, as disclosed herein.

In some embodiments, the first emissive region is configured to emit a light having a peak wavelength λ_max1; the second emissive region is configured to emit a light having a peak wavelength λ_max2. In some embodiments, the difference between the peak wavelengths λ_max1 and λ_max2 is at least 4 nm but within the same color. For example, a light blue and a deep blue light as described above. In some embodiments, a first emissive region is configured to emit a light having a peak wavelength λ_max1 in one region of the visible spectrum of 400-500 nm, 500-600 nm, 600-700 nm; and a second emissive region is configured to emit light having a peak wavelength λ_max2 in one of the remaining regions of the visible spectrum of 400-500 nm, 500-600 nm, 600-700 nm. In some embodiments, the first emissive region comprises a first number of emissive layers that are deposited one over the other if more than one; and the second emissive region comprises a second number of emissive layers that is deposited one over the other if more than one; and the first number is different from the second number. In some embodiments, both the first emissive region and the second emissive region comprise a phosphorescent materials, which may be the same or different. In some embodiments, the first emissive region comprises a phosphorescent material, while the second emissive region comprises a fluorescent material. In some embodiments, both the first emissive region and the second emissive region comprise a fluorescent materials, which may be the same or different.

In some embodiments, the at least one pixel of the OLED or emissive regions includes a total of N subpixels; wherein the N subpixels comprises the first subpixel and the second subpixel; wherein each of the N subpixels comprises an emissive region; wherein the total number of the emissive regions within the at least one pixel is equal to or less than N−1. In some embodiments, the second emissive region is exactly the same as the first emissive region; and each subpixel of the at least one pixel comprises the same one emissive region as the first emissive region. In some embodiments, the full-color pixel arrangements can have a plurality of pixels comprising a first pixel region and a second pixel region; wherein at least one display characteristic in the first pixel region is different from the corresponding display characteristic of the second pixel region, and wherein the at least one display characteristic is selected from the group consisting of resolution, cavity mode, color, outcoupling, and color filter.

In some embodiments, the OLED is a stacked OLED comprising one or more charge generation layers (CGLs). In some embodiments, the OLED comprises a first electrode, a first emissive region disposed over the first electrode, a first CGL disposed over the first emissive region, a second emissive region disposed over the first CGL, and a second electrode disposed over the second emissive region. In some embodiments, the first and/or the second emissive regions can have the various device characteristics as described above for the pixelated device. In some embodiments, the stacked OLED is configured to emit white color. In some embodiments, one or more of the emissive regions in a pixelated or in a stacked OLED comprises a sensitizer and an acceptor with the various sensitizing device characteristics and the various embodiments of the inventive compounds disclosed herein. For example, the first emissive region is comprised in a sensitizing device, while the second emissive region is not comprised in a sensitizing device; in some instances, both the first and the second emissive regions are comprised in sensitizing devices.

In some embodiments, the OLED can emit light having at least 1%, 5%, 10, 30%, 50%, 70%, 80%, 90%, 95%, 99%, or 100% from the plasmonic mode. In some embodiments, at least one of the anode, the cathode, or a new layer disposed over the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to non-radiative mode of surface plasmon polariton. In some embodiments, the enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer. A threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. Another threshold distance is the distance at which the total radiative decay rate constant divided by the sum of the total non-radiative decay rate constant and total radiative decay rate constant is equal to the photoluminescent yield of the emissive material without the enhancement layer present.

In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on a side opposite the organic emissive layer The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for intervening layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials.

The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and a reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides, or the enhancement layer itself being as the CGL, results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs.

In some embodiments, the enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. In some embodiments, the plasmonic material includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, or Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly.

In some embodiments, the outcoupling layer has wavelength-sized or sub-wavelength sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles. In some embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed over a material. In these embodiments the outcoupling layer may be tunable by at least one of: varying a size of the plurality of nanoparticles, varying a shape of the plurality of nanoparticles, changing a material of the plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material, adding an additional layer disposed on the plurality of nanoparticles, varying a thickness of the enhancement layer, or varying the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, and Ca, alloys or mixtures of these materials, and stacks of these materials. In some embodiments the outcoupling layer is formed by lithography.

In some embodiments of plasmonic device, the emitter, and/or host compounds used in the emissive layer has a vertical dipole ratio (VDR) of 0.33 or more. In some such embodiments, the emitter, and/or host compounds have a VDR of 0.40, 0.50, 0.60, 0.70, or more.

In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound or a formulation of the compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound comprising two or more carbene atoms and at least one deuterium atom; or a compound comprising a tetradentate ligand L_A, wherein L_A comprises a first moiety and a second moiety; the first moiety and the second moiety are both heterocyclic carbene ligands, and wherein at least the first moiety comprises Formula I as defined herein; or a compound comprising a first ligand L_A′ of Formula II as defined herein.

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, and an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized as an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer (HIL) 120, a hole transport layer (HTL) 125, an electron blocking layer (EBL) 130, an emissive layer (EML) 135, a hole blocking layer (HBL) 140, an electron transport layer (ETL) 145, an electron injection layer (EIL) 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the present disclosure may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation, sputtering, chemical vapor deposition, atomic layer deposition, and electron beam deposition. Preferred patterning methods include deposition through a mask, photolithography, and cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a plurality of alternative layers of polymeric material and non-polymeric material; organic material and inorganic material; or a mixture of a polymeric material and a non-polymeric material as one example described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties.

Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes. In some embodiments, the OLED further comprises one or more quantum dots. Such quantum dots can be in the emissive layer, or in other functional layers, such as a down conversion layer.

In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.

D. Other Materials Used in the OLED

The materials described herein are as various examples useful for a particular layer in an OLED. They may also be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used by themselves in the EML, or in conjunction with a wide variety of other emitters, hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds and the devices disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

a) Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer. In some embodiments, conductivity dopants comprises at least one chemical moiety selected from the group consisting of cyano, fluorinated aryl or heteroaryl, fluorinated alkyl or cycloalkyl, alkylene, heteroaryl, amide, benzodithiophene, and highly conjugated heteroaryl groups extended by non-ring double bonds.

b) HIL/HTL:

A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each of Ar¹ to Ar⁹ may be unsubstituted or may be substituted by a general substituent as described above, any two substituents can be joined or fused into a ring.

In some embodiments, each Ar¹ to Ar⁹ independently comprises a moiety selected from the group consisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C or N; Z¹⁰¹ is C, N, O, or S.

Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40; (Y¹⁰¹-Y¹⁰²) is a bidentate ligand, the coordinating atoms of Y¹⁰¹ and Y¹⁰² are independently selected from C, N, O, P, and S; L¹⁰¹ is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In some embodiments, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine or 2-phenylimidazole derivative. In some embodiments, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In some embodiments, Met is selected from Ir, Pt, Pd, Os, Cu, and Zn. In some embodiments, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

In some embodiments, the HIL/HTL material is selected from the group consisting of phthalocyanine and porphryin compounds, starburst triarylamines, CFx fluorohydrocarbon polymer, conducting polymers (e.g., PEDOT:PSS, polyaniline, polypthiophene), phosphonic acid and sliane SAMs, triarylamine or polythiophene polymers with conductivity dopants, Organic compounds with conductive inorganic compounds (such as molybdenum and tungsten oxides), n-type semiconducting organic complexes, metal organometallic complexes, cross-linkable compounds, polythiophene based polymers and copolymers, triarylamines, triaylamine with spirofluorene core, arylamine carbazole compounds, triarylamine with (di)benzothiophene/(di)benzofuran, indolocarbazoles, isoindole compounds, and metal carbene complexes.

c) EBL:

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more emitters closest to the EBL interface. In some embodiments, the compound used in EBL contains at least one carbazole group and/or at least one arylamine group. In some embodiments the HOMO level of the compound used in the EBL is shallower than the HOMO level of one or more of the hosts in the EML. In some embodiments, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described herein.

d) Hosts:

The light emitting layer of the organic EL device of the present disclosure preferably contains at least a light emitting material as the dopant, and a host material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the host won't fully quench the emission of the dopant.

Examples of metal complexes used as host are preferred to have the following general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, the coordinating atoms of Y¹⁰³ and Y¹⁰⁴ are independently selected from C, N, O, P, and S; L¹⁰¹ is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In some embodiments, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In some embodiments, Met is selected from Ir and Pt. In a further embodiments, (Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

In some embodiments, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-carbazole, aza-indolocarbazole, aza-triphenylene, aza-tetraphenylene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by the general substituents as described herein or may be further fused.

In some embodiments, the host compound comprises at least one of the moieties selected from the group consisting of:

wherein k is an integer from 0 to 20 or 1 to 20. X¹⁰¹ to X¹⁰⁸ are independently selected from C or N. Z¹⁰¹ and Z¹⁰² are independently selected from C, N, O, or S.

In some embodiments, the host material is selected from the group consisting of arylcarbazoles, metal 8-hydroxyquinolates, (e.g., alq3, balq), metal phenoxybenzothiazole compounds, conjugated oligomers and polymers (e.g., polyfluorene), aromatic fused rings, zinc complexes, chrysene based compounds, aryltriphenylene compounds, poly-fused heteroaryl compounds, donor acceptor type molecules, dibenzofuran/dibenzothiophene compounds, polymers (e.g., pvk), spirofluorene compounds, spirofluorene-carbazole compounds, indolocabazoles, 5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole), tetraphenylene complexes, metal phenoxypyridine compounds, metal coordination complexes (e.g., Zn, Al with N{circumflex over ( )}N ligands), dibenzothiophene/dibenzofuran-carbazole compounds, silicon/germanium aryl compounds, aryl benzoyl esters, carbazole linked by non-conjugated groups, aza-carbazole/dibenzofuran/dibenzothiophene compounds, and high triplet metal organometallic complexes (e.g., metal-carbene complexes).

e) Emitter Materials in EML:

One or more emitter materials may be used in conjunction with the compound or device of the present disclosure. The emitter material can be emissive or non-emissive in the current device as described herein. Examples of the emitter materials are not particularly limited, and any compounds may be used as long as the compounds are capable of producing emissions in a regular OLED device. Examples of suitable emitter materials include, but are not limited to, compounds which are capable of producing emissions via phosphorescence, non-delayed fluorescence, delayed fluorescence, especially the thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.

In some embodiments, the emitter material has the formula of M(L¹)_x(L²)_y(L³)_z;

• • wherein L¹, L², and L³ can be the same or different;
  • wherein x is 1, 2, or 3;
  • wherein y is 0, 1, or 2;
  • wherein z is 0, 1, or 2;
  • wherein x+y+z is the oxidation state of the metal M;
  • wherein L¹ is selected from the group consisting of the structures of LIGAND LIST:

wherein each L² and L³ are independently selected from the group consisting of

and the structures of LIGAND LIST; wherein:

• • M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Zn, Au, Ag, and Cu;
  • T is selected from the group consisting of B, Al, Ga, and In;
  • K^1′ is a direct bond or is selected from the group consisting of NR_e, PR_e, O, S, and Se;
  • each Y¹ to Y¹⁵ are independently selected from the group consisting of carbon and nitrogen;
  • Y′ is selected from the group consisting of BR_e, NR_e, PR_e, O, S, Se, C═O, S═O, SO₂, CR_eR_f, SiR_eR_f, and GeR_eR_f;
  • each R_a, R_b, R_c, and R_d can independently represent from mono to the maximum possible number of substitutions, or no substitution;
  • each R_a1, R_b1, R_c1, R_d1, R_a, R_b, R_c, R_d, R_e, and R_f is independently a hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; and
    wherein any two substituents can be fused or joined to form a ring or form a multidentate ligand.

In some embodiments, the emitter material is selected from the group consisting of the following Dopant Group 1:

wherein
each of X⁹⁶ to X⁹⁹ is independently C or N;
each Y¹⁰⁰ is independently selected from the group consisting of a NR″, O, S, and Se;
each of R^10a, R^20a, R^30a, R^40a, and R^50a independently represents mono substitution, up to the maximum substitutions, or no substitution; each of R, R′, R″, R^10a, R^11a, R^12a, R^13a, R^20a, R^30a, R^40a, R^50a, R⁶⁰, R⁷⁰, R⁹⁷, R⁹⁸, and R⁹⁹ is independently a hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; any two substituents can be joined or fused to form a ring.

In some embodiments, the emitter material is selected from the group consisting of the following Dopant Group 2:

wherein:

• • each Y¹⁰⁰ is independently selected from the group consisting of a NR″, O, S, and Se;
  • L is independently selected from the group consisting of a direct bond, BR″, BR″R″′, NR″, PR″, O, S, Se, C═O, C═S, C═Se, C═NR″, C═CR″R″′, S═O, SO₂, CR″, CR″R″′, SiR″R″′, GeR″R″′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;
  • X¹⁰⁰ and X²⁰⁰ for each occurrence is selected from the group consisting of O, S, Se, NR″, and CR″R″′;
  • each R^A″, R^B″, R^C″, R^D″, R^E″, and R^F″ independently represents mono-, up to the maximum substitutions, or no substitutions;
    each of R, R′, R″, R″′, R^A1′, R^A2′, R^A″, R^B″, R^C″, R^D″, R^E″, R^F″, R^G″, R^H″, R^I″, R^J″, R^K″, R^L″, R^M″, and R^N″ is independently a hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; any two substituents can be joined or fused to form a ring;

In some embodiments of the above Dopant Groups 1 and 2, each unsubstituted aromatic carbon atom can be replaced with N to form an aza-ring. In some embodiments, the maximum number of N atom in one ring is 1 or 2. In some embodiments of the above Dopant Groups 2, Pt atom in each formula can be replaced by Pd atom.

In some embodiments of the OLED, the delayed fluorescence material comprises at least one donor group and at least one acceptor group. In some embodiments, the delayed fluorescence material is a metal complex. In some embodiments, the delayed fluorescence material is a non-metal complex. In some embodiments, the delayed fluorescence material is a Zn, Cu, Ag, or Au complex.

In some embodiments of the OLED, the delayed fluorescence material has the formula of M(L⁵)(L⁶), wherein M is Cu, Ag, or Au, L⁵ and L⁶ are different, and L⁵ and L⁶ are independently selected from the group consisting of:

wherein A¹-A⁹ are each independently selected from C or N;
each R^P, R^Q, and R^U independently represents mono-, up to the maximum substitutions, or no substitutions;
wherein each R^P, R^P, R^U, R^SA, R^SB, R^RA, R^RB, R^RC, R^RD, R^RE, and R^RF is independently a hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; any two substituents can be joined or fused to form a ring.

In some embodiments of the OLED, the delayed fluorescence material comprises at least one of the donor moieties selected from the group consisting of:

wherein Y^T, Y^U, Y^V, and Y^W are each independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO₂.

In some of the above embodiments, any carbon ring atoms up to maximum of a total number of three, together with their substituents, in each phenyl ring of any of above structures can be replaced with N.

In some embodiments, the delayed fluorescence material comprises at least one of the acceptor moieties selected from the group consisting of nitrile, isonitrile, borane, fluoride, pyridine, pyrimidine, pyrazine, triazine, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-triphenylene, imidazole, pyrazole, oxazole, thiazole, isoxazole, isothiazole, triazole, thiadiazole, and oxadiazole. In some embodiments, the acceptor moieties and the donor moieties as described herein can be connected directly, through a conjugated linker, or a non-conjugated linker, such as a sp³ carbon or silicon atom.

In some embodiments, the fluorescent material comprises at least one of the chemical moieties selected from the group consisting of:

wherein Y^F, Y^G, Y^H, and Y^I are each independently selected from the group consisting of B, C, Si, Ge, N, P, O, S, Se, C═O, S═O, and SO₂.
wherein X^F and X^G are each independently selected from the group consisting of C and N.

In some of the above embodiments, any carbon ring atoms up to maximum of a total number of three, together with their substituents, in each phenyl ring of any of above structures can be replaced with N.

f) HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further away from the vacuum level) and/or higher triplet energy than one or more of the emitters closest to the HBL interface.

In some embodiments, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In some embodiments, compound used in HBL comprises at least one of the following moieties selected from the group consisting of:

wherein k is an integer from 1 to 20; L¹⁰¹ is another ligand, k′ is an integer from 1 to 3.

g) ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In some embodiments, compound used in ETL comprises at least one of the following moieties in the molecule:

and fullerenes; wherein k is an integer from 1 to 20, X¹⁰¹ to X¹⁰⁸ is selected from C or N; Z¹⁰¹ is selected from the group consisting of C, N, O, and S.

In some embodiments, the metal complexes used in ETL contains, but not limit to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

In some embodiments, the ETL material is selected from the group consisting of anthracene-benzoimidazole compounds, aza triphenylene derivatives, anthracene-benzothiazole compounds, metal 8-hydroxyquinolates, metal hydroxybenoquinolates, bathocuprine compounds, 5-member ring electron deficient heterocycles (e.g., triazole, oxadiazole, imidazole, benzoimidazole), silole compounds, arylborane compounds, fluorinated aromatic compounds, fullerene (e.g., C60), triazine complexes, and Zn (N{circumflex over ( )}N) complexes.

h) Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen of the compound being deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. As used herein, percent deuteration has its ordinary meaning and includes the percent of all possible hydrogen and deuterium atoms that are replaced by deuterium atoms. In some embodiments, the deuterium atoms are attached to an aromatic ring. In some embodiments, the deuterium atoms are attached to a saturated carbon atom, such as an alkyl or cycloalkyl carbon atom. In some other embodiments, the deuterium atoms are attached to a heteroatom, such as Si, or Ge atom.

It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.

EXPERIMENTAL SECTION

The inventive Compound A could be synthesized according to literature procedures. By treating the commercial starting material 1,3-di(1H-imidazol-1-yl)benzene with (3,5-di-tert-butylphenyl)boronic acid and (2-methoxyphenyl)boronic acid subsequently in the presence of catalytic copper acetate, 1 and 2 could be obtained (J. Org. Chem. 2013, 78, 5723), respectively. After demethylation of the methoxy group using the known procedure, Compound A could be synthesized upon platination such as disclosed in EP2891659A2.

TABLE 1
DFT Calculation
		T1	HOMO	LUMO
Name	Structure	(nm)	(eV)	(eV)
Compound A		474	−5.3	−1.55
Compound B		517	−5.34	−1.92
Compound C		516	−5.22	−1.76
Compound D		520	−5.28	−1.82
Compound E		612	−5.61	−2.83
Compound F		564	−5.53	−2.51
Compound G		500	−5.29	−1.75
Compound H		491	−5.32	−1.77
Compound I		480	−5.23	−1.54
Compound J		482	−5.44	−1.90
Compound K		479	−5.33	−1.78
Compound L		502	−5.40	−1.88

Table 1 summarizes the DFT calculations of Ti, HOMO, LUMO for inventive compounds A-L. By different molecular design, it covers a wide range of T1 energies ranging from blue to red with tunable HOMO and LUMO levels, allowing them to be excellent candidates for PhOLED applications.

Calculations were performed using the B3LYP functional with a CEP-31G basis set. Geometry optimizations were performed in vacuum. Excitation energies were obtained at these optimized geometries using time-dependent density functional theory (TDDFT). A continuum solvent model was applied in the TDDFT calculation to simulate tetrahydrofuran solvent. All calculations were carried out using the program Gaussian.

The calculations obtained with the above-identified DFT functional set and basis set are theoretical. Computational composite protocols, such as Gaussian with the 6-31 G* basis set used herein (or CEP-31 G basis set which may be used for organometallic molecules), rely on the assumption that electronic effects are additive and, therefore, larger basis sets can be used to extrapolate to the complete basis set (CBS) limit. However, when the goal of a study is to understand variations in HOMO, LUMO, S₁, T₁, bond dissociation energies, etc. over a series of structurally-related compounds, the additive effects are expected to be similar. Accordingly, while absolute errors from using the B3LYP may be significant compared to other computational methods, the relative differences between the HOMO, LUMO, S₁, T₁, and bond dissociation energy values calculated with B3LYP protocol are expected to reproduce experiment quite well. See, e.g., Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and Supplemental Information (discussing the reliability of DFT calculations in the context of OLED materials). Moreover, with respect to iridium or platinum complexes that are useful in the OLED art, the data obtained from DFT calculations correlates very well to actual experimental data. See Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing DFT calculations closely correlating with actual data for a variety of emissive complexes); Morello, G. R., J. Mol. Model. 2017, 23:174 (studying of a variety of DFT functional sets and basis sets and concluding the combination of B3LYP and CEP-31G is particularly accurate for emissive complexes).

Claims

1. A compound comprising two or more carbene atoms coordinated to Pt(II) or Pd(II);

wherein the compound comprises at least one deuterium atom; and

with the proviso that the compound is not:

2. The compound of claim 1, wherein the two carbene atoms are trans or cis; and/or wherein the compound comprises four metal-carbon bonds or wherein the compound comprises at least one metal-oxygen bond; and/or wherein the compound comprises at least one deuterated alkyl group or deuterated phenyl group.

3. The compound of claim 1, wherein the compound is selected from the group consisting of:

wherein RA, RB, RC, RD, and RE each independently represent mono to the maximum allowable substitution, or no substitution;

wherein each of R, R′, RA, RB, RC, RD, and RE is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;

wherein X1—X5 are each independently C or N;

L is selected from the group consisting of a direct bond, BR, BRR′, NR, PR, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO2, CR, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

each of L1 and L2 is independently absent or selected from the group consisting of BR, BRR′, NR, PR, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO2, CR, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof;

any two substituents can be joined or fused to form a ring; and

at least one of R, R′, RA, RB, RC, RD, and RE is or comprises a deuterium atom.

4. The compound of claim 1, wherein the compound is selected from the group consisting of Table A defined below: TABLE A LA Structure of LA LA1-(Ri)(Lm)(Ln), wherein LA1- (R1)(L1)(L1) to LA1-(R445) (L29)(L29), having the structure LA2-(Ri)(Lm)(Ln), wherein LA2-(R1) (L1)(L1) to LA2-(R445) (L29)(L29), having the structure LA3-(Ri)(Lm)(Ln), wherein LA3- (R1)(L1)(L1) to LA3-(R445) (L29)(L29), having the structure LA4-(Ri)(Lm)(Ln), wherein LA4- (R1)(L1)(L1) to LA4-(R445) (L29)(L29), having the structure LA5-(Ri)(Lm) (Ln)(Lo), wherein LA5- (R1)(L1)(L1) (L1) to LA5- (R445)(L29) (L29)(L29), having the structure LA6-(Ri)(Lm) (Ln)(Lo), wherein LA6- (R1)(L1)(L1) (L1) to LA6- (R445)(L29) (L29)(L29), having the structure LA7-(Ri)(Lm) (Ln)(Lo), wherein LA7- (R1)(L1)(L1) (L1) to LA7- (R445)(L29) (L29)(L29), having the structure LA8-(Ri)(Lm) (Ln)(Lo), wherein LA8- (R1)(L1)(L1) (L1) to LA8- (R445)(L29) (L29)(L29), having the structure

wherein i, j, k, and l, are each independently an integer from 1 to 445, wherein R1 to R445 have the structures as defined in LIST 5; and

wherein m and n are each independently an integer from 1 to 29, wherein L1 to L29 have the structures as defined LIST 6.

5. The compound of claim 1, wherein the compound is selected from the group consisting of:

6. A monometallic compound comprising a tetradentate ligand LA, wherein:

LA is coordinated to a metal M, which is selected from the group consisting of Pt, Pd, Cu, Ag, and Au;

LA comprises a first moiety and a second moiety;

the first moiety and the second moiety are both heterocyclic carbene ligands, which coordinate to M through metal-carbene bonds;

wherein at least the first moiety comprises Formula I:

wherein the dashed line indicates a carbene bond to M;

wherein the wavy line indicates the remaining part of the tetradentate ligand LA;

wherein RA and RB each independently represent mono to the maximum allowable substitution, or no substitution;

wherein each RA and RB is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;

wherein X1—X5 are each independently C or N;

wherein X1—X5 is C if attached to an RA substituent;

wherein at least one of the following is true:

(1) at least one RA is selected from the group consisting of deuterium, aryl, heteroaryl, cycloalkyl, and cycloheteroalkyl, and combinations thereof, and is attached to X1 or X5;

(2) at least one RA comprises deuterium, silicon, boron, or selenium;

wherein any two substituents may be joined or fused to form a ring; and

wherein the compound does not comprise the structure:

 wherein R is a methyl or a phenyl group.

7. The compound of claim 6, wherein all of X1—X5 are C or wherein at least one of X1—X5 is N.

8. The compound of claim 6, wherein the ligand LA is selected from the group consisting of:

wherein each L is independently selected from LIST 1 consisting of:

wherein each L1 and L2 is independently selected from LIST 2 consisting of:

absent,

wherein RA, RB, RC, RD, and RE each independently represent mono to the maximum allowable substitution, or no substitution;

wherein each R, R′, RA, RB, RC, RD, and RE is independently selected from the groups of LIST 3 as defined herein.

9. The claim of claim 8, wherein at least one of R, R′, RA, RB, RC, RD, and RE is independently selected from LIST 4 consisting of:

wherein each of QA, QB, QC, QD, an QE independently represents mono to the maximum allowable substitution, or no substitution;

wherein each QA, QB, QC, QD, QE, QA1, QB1, QC1, QD1 an QE1 is independently a hydrogen or a substituent selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;

each Yaa and Ybb is independently selected from the group consisting of a direct bond, BR, BRR′, NR, PR, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO2, CR, CRR′, SiRR′, GeRR′, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof; and any two substituents can be joined or fused to form a ring.

10. The compound of claim 6, wherein the ligand LA is selected from the group consisting of Table B, and Table C below: TABLE B LA Structure of LA LA9-(Ri)(Rj)(Lm)(Ln), wherein LA9- (R29)(R1)(L1)(L1) to LA9- (R445)(R445)(L29)(L29), having the structure LA10- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA10- (R29)(R1)(R1)(L1)(L1) to LA10- (R445)(R445)(R445)(L29) (L29), having the structure LA11- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA11- (R29)(R1)(R1)(L1)(L1) to LA11- (R445)(R445)(R445)(L29) (L29), having the structure LA12-(Ri)(Rj)(Lm)(Ln), wherein LA12- (R29)(R1)(L1)(L1) to LA12- (R445)(R445)(L29)(L29), having the structure LA13- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA13- (R29)(R1)(R1)(L1)(L1) to LA13- (R445)(R445)(R445)(L29) (L29), having the structure LA14- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA14- (R29)(R1)(R1)(L1)(L1) to LA14- (R445)(R445)(R445)(L29) (L29), having the structure LA15-(Ri)(Rj)(Lm)(Ln), wherein LA15- (R29)(R1)(L1)(L1) to LA15- (R445)(R445)(L29)(L29), having the structure LA16- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA16- (R29)(R1)(R1)(L1)(L1) to LA16- (R445)(R445)(R445)(L29) (L29), having the structure LA17- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA17- (R29)(R1)(R1)(L1)(L1) to LA17- (R445)(R445)(R445)(L29) (L29), having the structure LA18-(Ri)(Rj)(Lm)(Ln), wherein LA18- (R29)(R1)(L1)(L1) to LA18- (R445)(R445)(L29)(L29), having the structure LA19- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA19- (R29)(R1)(R1)(L1)(L1) to LA19- (R445)(R445)(R445)(L29) (L29), having the structure LA20- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA20- (R29)(R1)(R1)(L1)(L1) to LA20- (R445)(R445)(R445)(L29) (L29), having the structure LA21- (Ri)(Rj)(Rk)(Lm)(Ln), wherein LA21- (R1)(R1)(R1)(L1)(L1) to LA21- (R445)(R445)(R445)(L29) (L29), having the structure LA22- (Ri)(Rj)(Rk)(RI)(Lm)(Ln), wherein LA22- (R1)(R1)(R1)(R1)(L1)(L1) to LA22- (R445)(R445)(R445) (R445)(L29)(L29), having the structure LA23- (Ri)(Rj)(Rk)(RI)(Lm)(Ln), wherein LA23- (R29)(R1)(R1)(R1)(L1)(L 1) to LA23- (R445)(R445)(R445) (R445)(L29)(L29), having the structure LA24- (Ri)(Rj)(Rk)(RI)(Lm)(Ln), wherein LA24- (R29)(R1)(R1)(R1)(L1)(L1) to LA24- (R445)(R445)(R445) (R445)(L29)(L29), having the structure TABLE C LA Structure of LA LA25-(Rp)(Rj)(Lm)(Ln), wherein LA25- (R203)(R1)(L1)(L1) to LA25- (R445)(R445)(L29)(L29), having the structure LA26-(Rp)(Rj)(Lm)(Ln), wherein LA26- (R203)(R1)(L1)(L1) to LA26- (R445)(R445)(L29)(L29), having the structure LA27-(Rp)(Rj)(Lm)(Ln), wherein LA27- (R203)(R1)(L1)(L1) to LA27- (R445)(R445)(L29)(L29), having the structure LA28-(Rp)(Rj)(Lm)(Ln), wherein LA28- (R203)(R1)(L1)(L1) to LA28- (R445)(R445)(L29)(L29), having the structure LA29-(Rp)(Rj)(Lm)(Ln), wherein LA29- (R203)(R1)(L1)(L1) to LA29- (R445)(R445)(L29)(L29), having the structure LA30-(Rp)(Rf)(Lm)(Ln), wherein LA30- (R203)(R1)(L1)(L1) to LA30- (R445)(R445)(L29)(L29), having the structure LA31-(Rp)(Rj)(Lm)(Ln), wherein LA31- (R203)(R1)(L1)(L1) to LA31- (R445)(R445)(L29)(L29), having the structure LA32-(Rp)(Rj)(Lm)(Ln), wherein LA32- (R203)(R1)(L1)(L1) to LA32- (R445)(R445)(L29)(L29), having the structure LA33-(Rp)(Rj)(Lm)(Ln), wherein LA33- (R203)(R1)(L1)(L1) to LA33- (R445)(R445)(L29)(L29), having the structure LA34-(Rp)(Rj)(Lm)(Ln), wherein LA34- (R203)(R1)(L1)(L1) to LA34- (R445)(R445)(L29)(L29), having the structure LA35-(Rp)(Rj)(Lm)(Ln), wherein LA35- (R203)(R1)(L1)(L1) to LA35- (R445)(R445)(L29)(L29), having the structure LA36-(Rp)(Rj)(Lm)(Ln), wherein LA36- (R203)(R1)(L1)(L1) to LA36- (R445)(R445)(L29)(L29), having the structure

wherein i, j, k, and l, are each independently an integer from 1 to 445, wherein R1 to R445 have the structures as defined in LIST 5; and

wherein m and n are each independently an integer from 1 to 29, wherein L1 to L29 have the structures as defined LIST 6.

11. The compound of claim 6, wherein the compound is selected from the group consisting of:

12. A compound comprising a first ligand LA′ of Formula II:

wherein RF, RG, and RH each independently represent mono to the maximum allowable substitution, or no substitution;

wherein each R1, R2, RF, RG, and RH is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;

wherein X6—X8 are each independently C or N;

LA′ is coordinated to a metal M via the dashed lines, which is selected from the group consisting of Pt, Pd, Cu, Ag, and Au;

wherein at one of R1 and R2 is coordinated to M such that LA′ is a tetradentate ligand; and

wherein any two substituents may be joined or fused to form a ring.

13. The compound of claim 12, wherein at least one of X6—X8 is N or wherein all of X6—X8 are C.

14. The compound of claim 12, wherein the ligand LA is selected from the group consisting of:

wherein R1 represents mono to the maximum allowable substitution, or no substitution;

wherein each R1 is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boryl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, selenyl, and combinations thereof;

wherein each L3, L4, and L5 is independently selected from LIST 2; wherein each RF, RG, RH, RI, and R′ is independently selected from LIST 3 and LIST 4;

the remaining variables are the same as previously defined, and

any two substituents can be joined or fused to form a ring.

15. The compound of claim 12, wherein the ligand LA′ is selected from the group consisting of: LA′ Structure of LA′ LA′1-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′1- (R1)(R1)(L1)(L1)(L1) to LA′1- (R445)(R445)(L29)(L29)(L29), having the structure LA′2-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′2- (R1)(R1)(L1)(L1)(L1) to LA′2- (R445)(R445)(L29)(L29)(L29), having the structure LA′.3-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′3- (R1)(R1)(L1)(L1)(L1) to LA′3- (R445)(R445)(L29)(L29)(L29), having the structure LA′4-(Ru)(Rv)(Lq)(Lr)(Ls), wherein LA′4- (R1)(R1)(R1)(L1)(L1)(L1) to LA′4- (R445)(R445)(R445)(L29)(L29)(L29), having the structure

wherein u and v are each independently an integer from 1 to 445, wherein R1 to R445 have the structures in LIST 5;

and wherein q, r, and s are each independently an integer from 1 to 29, wherein L1 to L29 have the structures in LIST 6.

16. The compound of claim 12, wherein the compound is selected from the group consisting of:

17. An organic light emitting device (OLED) comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode,

wherein the organic layer comprises a compound according to claim 1.

18. The OLED of claim 17, wherein the organic layer further comprises a host, wherein the host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 512-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-512-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).

19. The OLED of claim 17, wherein the organic layer further comprises a host, wherein the host is selected from the group consisting of:

wherein:

each of X1 to X24 is independently C or N; L′ is a direct bond or an organic linker;

each YA is independently selected from the group consisting of absent a bond, O, S, Se, CRR′, SiRR′, GeRR′, NR, BR, BRR′; each of RA′, RB′, RC′, RD′, RE′, RF′, and RG′ independently represents mono, up to the maximum substitutions, or no substitutions;

each of R, R′, RA′, RB′, RC′, RD′, RE′, RF′, and RG′ is independently a hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, and combinations thereof;

two adjacent of RA′, RB′, RC′, RD′, RE′, RF′, and RG′ are optionally joined or fused to form a ring.

20. A consumer product comprising an organic light-emitting device (OLED) comprising:

an anode;

a cathode; and

an organic layer disposed between the anode and the cathode,

wherein the organic layer comprises a compound according to claim 1.